Catalyst for bisalkoxycarbonylation of olefins, and method for production of succinate derivatives

ABSTRACT

A catalyst for the bisalkoxycarbonylation of olefins comprising a noble metal compound and a phosphine chalcogenide of the following formula (1):                    
     wherein each of R 1 , R 2  and R 3  is, independently, an alkyl group or an aryl group each of which may have a substituent, and A is a Group 16 element of the Periodic Table; and R 1 , R 2  or R 3  may be combined, directly or through a bridging group, with one another where the groups to be combined may be attached either to an identical phosphorus atom or to different phosphorus atoms. Element A includes oxygen, sulfur and selenium atoms. The noble metal compound includes palladium(II) halides and other palladium compounds. The catalyst may further include a copper(I) halide or other copper compound as a co-catalyst. The use of this catalyst can provide the bisalkoxycarbonylation of olefins with efficiency.

This application is a divisional of application Ser. No. 09/406,139,filed on Sep. 27, 1999, which is a divisional of application Ser. No.09/332,072, filed on Jun. 14, 1999, now U.S. Pat. No. 6,159,891, theentire contents of each are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to catalysts used for thebisalkoxycarbonylation of olefins, to novel phosphine chalcogenideswhich are useful as ligands of the catalysts, to processes for thebisalkoxycarbonylation of olefins using the catalysts, and to methodsfor production of succinate derivatives.

2. Description of the Prior Art

Processes for the alkoxycarbonylat ion of olefins have been proposed in(1) J. Am. Chem. Soc., 98, 1806(1976); (2) J. Mol. Cat. A: Chemical 111,L3-L6(1996); (3) J. Chem. Soc. Perkin Trans., 1031(1993); (4) J. Org.Chem., 57, 4189(1992), and satisfactory results have been achieved bythese processes.

For the bisalkoxycarbonylation of olefins, processes have been reportedin documents (5) J. Org. Chem., 37, 2034(1972),; (6) J. Am. Chem. Soc.,98, 1806(1976); (7) Bull. Chem. Soc. Jpn., 64, 3600(1991); (8)Tetrahedron Lett., 28, 325(1987); (9) J. Am. Chem. Soc., 98, 1810(1976);(10) Angew. Chem. Int. Ed. Engl., 32, 1719(1993); and (11)Organometallics, 11, 1975(1992). These processes are, however,respectively disadvantageous: The processes in the documents (5) and (6)are low in yield, the process in the document (7) gives a mixture of amonoalkoxycarbonylated compound and a bisalkoxycarbonylated compound,the process in the document (8) requires the addition of tetramethylureaor propylene oxide and ethyl ortho-acetate, the process in the document(9) should be conducted under high pressure conditions (3 atm),processes in the documents (10) and (11) accompany oligomerization.

In a document (12) Bull. Chem. Soc. Jpn., 69, 735(1996) is disclosed theuse of an optically active bisoxazoline as a ligand in thebisalkoxycarbonylation to obtain an optically active substance. Thisprocess requires a long time for the reaction and is low in reactivity.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide acatalyst which can catalyze the bisalkoxycarbonylation of olefins withefficiency.

It is another object of the invention to provide a novel phosphinechalcogenide compound which is useful as a ligand in a catalyst for theasymmetric bisalkoxycarbonylation of olefins.

A further object of the invention is to provide an efficient process forthe bisalkoxycarbonylation of olefins.

It is a yet another object of the invention to provide a process bywhich corresponding succinate derivatives can be obtained from olefinsin high yields under moderate conditions.

The present inventors made intensive investigations to achieve the aboveobjects, and found that the use of a noble metal compound catalystincluding a phosphine chalcogenide as a ligand can catalyze thebisalkoxycarbonylation of olefins with efficiency. The invention hasbeen accomplished based upon the finding.

To be more specific, the invention provides, in an aspect, a catalystfor the bisalkoxycarbonylation of olefins comprising a phosphinechalcogenide and a noble metal compound, the phosphine chalcogenidebeing of the following formula (1)

wherein R¹, R² and R³ are, independently, an alkyl group or an arylgroup each of which may have a substituent, and A is a Group 16 elementof the Periodic Table; R¹, R² or R³ may be combined, directly or througha bridging group, with one another where the groups to be combined maybe attached either to an identical phosphorus atom or to differentphosphorus atoms.

The element A may include, for example, an oxygen atom, a sulfur atomand a selenium atom. As examples of the phosphine chalcogenide, theremay be mentioned triphenylphosphine oxide, triphenylphosphine sulfide,triphenylphosphine selenide,2,2′-bis(diphenylthiophosphoryl)-1,1′-binaphthyl,2,3-bis(diphenylthiophosphoryl)butane, and2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis (diphenylthiophosphoryl)butane. The noble metal compound may include palladium compounds, forinstance.

The catalyst for the bisalkoxycarbonylation of olefins may furtherinclude a co-catalyst such as a copper catalyst. By way of illustration,the catalyst can include a palladium(II) halide as a noble metalcompound and a copper(I) halide as a co-catalyst.

The present invention provides, in another aspect, an optically active2,2′-bis(diphenylchalcogenophosphoryl)-1,1′-binaphthyl of the followingformula (1a):

wherein A¹ is a Group 16 element of the Periodic Table other thanoxygen; an optically active 2,3-bis(diphenylchalcogenophosphoryl)butaneof the following formula (1b):

wherein A² is a Group 16 element of the Periodic Table other thanoxygen; and an optically active2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylchalcogenophosphoryl)butaneof the following formula (1c):

wherein A³ is a Group 16 element of the Periodic Table other thanoxygen.

In a further aspect, the invention provides a process for thebisalkoxycarbonylation of olefins, which includes reacting an olefinwith an alcohol, oxygen and carbon monoxide in the presence of theaforementioned catalyst for the bisalkoxycarbonylation of olefins.

In addition and advantageously, the invention provides a method ofproducing a succinate derivative, which comprises reacting an olefinwith an alcohol, oxygen and carbon monoxide in the presence of theaforementioned catalyst to give a corresponding succinate derivative.

The method just mentioned above may preferably include a method composedof reacting an olefin of the following formula (2):

wherein each of R⁴, R⁵ and R⁶ is, independently, a hydrogen atom, analkyl group or an aryl group each of which may have a substituent, or asubstituted silyl group; at least two of R⁴, R⁵ and R⁶ may together forma ring with the adjacent carbon atom or carbon-carbon double bond, withan alcohol of the following formula (3):

 R⁷—OH  (3)

wherein R⁷ is an alkyl group, cycloalkyl group or aryl group each ofwhich may have a substituent, oxygen and carbon monoxide to give asuccinate derivative of the following formula (4):

wherein R⁴, R⁵, R⁶ and R⁷ have the same meanings as defined above. Asthe olefin, use may be made of, for example, any olefin where R⁴ is ahydrogen atom or an alkyl group which may have a substituent, either oneof R⁵ and R⁶ is a hydrogen atom or an alkyl group which may have asubstituent, and the other is an aryl group which may have a substituentor a substituted silyl group, and R⁴ and R⁶ may together form a ringwith the adjacent carbon-carbon double bond.

The method of producing a succinate derivative may be a method whichincludes reacting an olefin capable of forming a chiral compound byreaction, with an alcohol, oxygen and carbon monoxide in the presence ofa catalyst containing an optically active phosphine chalcogenide to givea corresponding optically active succinate derivative.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The catalyst for the bisalkoxycarbonylation of olefins according to theinvention is composed of a phosphine chalcogenide of the formula (1) anda noble metal compound. In the formula (1), the alkyl groups in R¹, R²and R³ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl and other straight chain alkyl groups; and isopropyl, isobutyl,sec-butyl, t-butyl and other branched chain alkyl groups. The carbonnumber of the alkyl group ranges, but not limited to, for example fromabout 1 to about 20, preferably from about 1 to about 10, and morepreferably from about 1 to about 4.

As the aryl group, there may be mentioned, for instance, phenyl group,naphthyl group (1-naphthyl group, 2-naphthyl group) and biphenyl group.The carbon number of the aryl group rages, but not limited to, fromabout 6 to about 18.

Each of the alkyl groups and aryl groups mentioned above may have asubstituent. Examples of the substituent include, aryl groups (e.g.,phenyl group, naphthyl group),alkyl groups (methyl, ethyl, propyl,isopropyl, butyl and other C₁-C₄ alkyl groups), cycloalkyl groups,halogen atoms (e.g., chlorine, bromine, iodine atoms), hydroxyl groupswhich may be protected with a protective group, mercapto groups whichmay be protected with a protective group, alkoxy groups (e.g., methoxy,ethoxy, propoxy, isopropoxy, butoxy and other C₁-C₄ alkoxy groups),alkylthio groups, nitro group, haloalkyl groups (e.g., trifluoromethylgroup, chloromethyl group, bromopropyl group and other halo-C₁-C₄ alkylgroups), carboxy groups which may be protected with a protective group,alkoxycarbonyl groups, aryloxycarbonyl groups, substituted orunsubstituted carbamoyl groups, amino groups which may be protected witha protective group, mono- or di-alkylamino groups, acylamino groups, andacyl groups. As the protective groups, any conventional protectivegroups in the area of organic synthesis can be employed.

The aforementioned R¹, R² or R³ may be combined, directly or through abridging group, with one another where the groups to be combined may beattached either to an identical phosphorus atom or to differentphosphorus atoms. Examples of such a group formed directly or through abridging group include methylene group, ethylene group,1,2-dimethylethylene group, propylene group, butylene group,2,3-O-isopropylidene-2,3-dihydroxybutylene group,1,1′-binaphthalen-2,2′-diyl group. Each of these groups may further havea substituent.

The Group 16 element of the Periodic Table shown by A in the formula (1)includes, for instance, oxygen, sulfur, selenium, tellurium, andpolonium atoms. Of these elements, oxygen Sulfur and selenium atoms arepreferred, among which a sulfur atom is particularly desirable.

The phosphine chalcogenide may be whichever of a chiral or achiralcompound, and when it is a chiral compound, it may be whichever of anoptically active substance or a racemic compound. The phosphinechalcogenide can be immobilized to or supported on an organic orinorganic carrier.

As typical examples of the phosphine chalcogenide, there may bementioned triphenylphosphine oxide, triphenylphosphine sulfide,triphenylphosphine selenide, tritolylphosphine sulfide,methyldiphenylphosphine sulfide, methyl(1-naphthyl)phenylphosphinesulfide, 1,2-bis(diphenylthiophosphoryl)ethane,1,4-bis(diphenylthiophosphoryl)butane,2,2′-bis(diphenylthiophosphoryl)-1,1′-binaphthyl,2,3-bis(diphenylthiophosphoryl)butane,2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphoryl)butane,2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylthiophosphoryl)butane,2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylselenophosphoryl)butane,and1,2-bis(diphenylthiophosphorylmethyl)-3,4-bis(2-methoxyphenyl)cyclobutane.

The optically active phosphine chalcogenide includes, for example,optically active substances of the compounds individually of theformulae (1a), (1b) and (1c), and optically active2,2′-bis(diphenylphosphoryl)-1,1′-binaphthyl, optically active2,3-bis(diphenylphosphoryl)butane, and optically active2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphoryl)butane.

The Group 16 element of the Periodic Table shown by A¹, A² and A³ in theformulae (1a), (1b) and (1c) includes sulfur, selenium, tellurium, andpolonium atoms, forexample. Of these elements, a sulfur atom or aselenium atom is preferred, among which a sulfur atom is particularlydesirable. A typical example of the optically active2,2′-bis(diphenylchalcogenophosphoryl)-1,1′-binaphthyl of the formula(la) includes (R)-2,2′-bis(diphenylthiophosphoryl)-1,1′-binaphthyl. Theoptically active 2,3-bis(diphenylchalcogenophosphoryl)butane of theformula (1b) typically includes, for example,(2R,3R)-2,3-bis(diphenylthiophosphoryl)butane. As typical examples ofthe optically active2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylchalcogenophosphoryl)butaneof the formula (1c), there may be mentioned(2R,3R)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylthiophosphoryl)butane,and(2R,3R)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylselenophosphoryl)butane.

An optically active compound of the formula (1a) can be obtained, forexample, by reacting an optically active2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) with an elementarysubstance of Group 16 element of the Periodic Table at, for example,room temperature in a proper solvent such as an ether, and isolating andpurifying the resultant substance by a conventional isolation techniquesuch as column chromatography or recrystallization. An optically activecompound of the formula (1b) can be prepared by, for example, reactingan optically active 2,3-bis (diphenylphosphino)butane (Chiraphos) withan elementary substance of Group 16 element of the Periodic Table at,for example, room temperature in a proper solvent such as an ether, andisolating and purifying the resultant substance by a conventionalisolation technique such as column chromatography or recrystallization.An optically active substance of the compound of the formula (1c) can beprepared by, for instance, reacting an optically active2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane(DIOP) with an elementary substance of Group 16 element of the PeriodicTable at, for example, room temperature in a proper solvent such asbenzene or acetone, and isolating and purifying the resultant substanceby a conventional isolation technique such as column chromatography orrecrystallization.

The noble metal in the noble metal compound includes, for example,ruthenium, rhodium, palladium, iridium, platinum, silver and gold. Asexamples of the noble metal compound, there may be mentioned simplesubstances of such noble metals, noble metal halides (e.g., chlorides,bromides, iodides), inorganic acid salts of noble metals, sulfonates ofnoble metals (e.g., trifluoromethanesulfonates), carboxylates of noblemetals, (e.g., acetates, trifluoroacetates), and complexes of thesesubstances. The noble metal compound (e.g., a simple substance of anoble metal) can be supported on an organic or inorganic carrier. Thevalency of the noble metal in the noble metal compound may usually be,but not limited to, zero or divalent, trivalent or tetravalent, andtypically divalent.

Of these noble metal compounds, palladium compounds are preferable.Typical examples of such palladium compounds include palladium-carbon,palladium-montmorillonite, allyl chloride palladium(II) dimer,palladium(II) halides [e.g., palladium(II) chloride, palladium(II)bromide, palladium(II) iodide], palladium(II) trifluoromethanesulfonate,palladium(II) acetate, palladium(II) trifluoroacetate, and complexes ofthese compounds. Among them, palladium(II) halides, in particularpalladium(II) chloride can advantageously be used.

The phosphine chalcogenide serves as a ligand for the noble metal in thecatalyst according to the invention. The invention is, therefore, alsodirected to noble metal complexes of the phosphine chalcogenide and tothe use of the complexes.

The catalyst of the invention can be composed of the phosphinechalcogenide, the noble metal compound and a co-catalyst. Theco-catalyst includes, for instance, copper compounds, iron compounds,manganese compounds, nitrites, and quinones, among which coppercompounds are preferred. As examples of the copper compounds, there maybe mentioned elementary copper; copper(II) chloride, copper(I) chloride,copper(I) bromide, copper(I) iodide and other copper halides; copper(II) trifluoromethanesulfonate, copper (I) trifluoromethanesulfonate andother copper sulfonates; copper(II) acetate, copper(I) acetate and othercopper carboxylates; copper thiocyanates; copper cyanides; and coppercomplexes. The copper compound (e.g., elementary copper) can besupported by an organic or inorganic carrier. The valency of copper mayusually be, but not limited to, monovalent or divalent. Of these coppercompounds, copper(I) chloride and other copper(I) halides canadvantageously be employed.

According to the process (method) of the invention, an olefin is reactedwith an alcohol, oxygen (molecular oxygen) and carbon monoxide in thepresence of the aforementioned catalyst. Examples of the olefins includea variety of compounds each having a non-aromatic carbon-carbon doublebond, such as aromatic olefins (aromatic vinyl compounds), vinylsilanes, aliphatic olefins, cyclic olefins (e.g., cyclic olefinsconjugated with an aromatic ring), and acrylic esters.

Of these olefins, typical examples are of the formula (2). The alkylgroup which may have a substituent and the aryl group which may have asubstituent in R⁴, R⁵ and R⁶ in the formula (2) include the alkyl groupsand aryl groups exemplified in the substituents R¹, R² and R³.

The substituted silyl groups in R⁴, R⁵ and R⁶ include groups of thefollowing formula (5):

wherein each of R⁸, R⁹ and R¹⁰ is an alkyl group or aryl group each ofwhich may have a substituent, an alkoxy group or a halogen atom. Thealkyl group which may have a substituent and the aryl group which mayhave a substituent in R⁸, R⁹ and R¹⁰ include the alkyl groups and arylgroups exemplified in the substituents R¹, R² and R³. Examples of thealkoxy group in R⁸, R⁹ and R¹⁰ include methoxy, ethoxy, propoxy,isopropoxy, butoxy, pentyloxy, hexyloxy and other C₁-C₆ alkoxy groups.The halogen atom includes, for instance, chlorine, bromine and iodineatoms. As typical examples of the substituted silyl group, there may bementioned dimethylphenylsilyl group and other tri-substituted silylgroups.

As the ring formed by at least two of R⁴, R⁵ and R⁶ together with theadjacent carbon atom or carbon-carbon double bond, there may bementioned cyclopentane ring, cyclohexane ring and other cycloalkanerings; cyclopentene ring, cyclohexene ring and other cycloalkene rings;indene ring, 1,2-dihydronaphthalene ring and other condensed hydrocarbonrings formed by condensing an aromatic ring (e.g., benzene ring) to aacycloalkene ring.

Of olefins of the formula (2), preferred are those in which R⁴ is ahydrogen atom or an alkyl group which may have a substituent (inparticular, a hydrogen atom or a C₁-C₄ alkyl group), either one of R⁵and R⁶ is a hydrogen atom or an alkyl group which may have a substituent(in particular, a hydrogen atom or a C₁-C₄ alkyl group), the other is anaryl group which may have a substituent or a substituted silyl group,and R⁴ and R⁶ may together form a ring with the adjacent carbon-carbondouble bond.

The alcohols include a variety of aliphatic alcohols, alicyclicalcohols, aromatic alcohols and phenols. The term “the alcohol” usedherein includes phenols as well as other alcohols for the sake ofconvenience. As the typical examples of the alcohols, there maybementioned compounds of the formula (3). Examples of the alkyl groupwhich may have a substituent and the aryl group which may have asubstituent in R⁷ in the formula (3) can be exemplified as the alkylgroups and aryl groups indicated in the substituent R¹, for example. Thecycloalkyl group includes, cyclopropyl, cyclopentyl, cyclohexyl, andcyclooctyl groups. These cycloalkyl groups may have a similarsubstituent as in the alkyl groups mentioned above.

Practical examples of the alcohols include methanol, ethanol, propanol,isopropyl alcohol, butanol, t-butyl alcohol, octanol and other aliphaticalcohols (e.g., aliphatic alcohols each having about 1 to 20 carbonatoms, preferably about 1 to 10 carbon atoms and more preferably about 1to 4 carbon atoms), cyclopentanol, cyclohexanol and other alicyclicalcohols; benzyl alcohol and other aromatic alcohols; and phenol, cresoland other phenols.

The amounts of the phosphine chalcogenide of the formula (1), the noblemetal compound and co-catalyst used in a reaction of the process(method) according to the invention are not particularly limited and canbe properly selected in consideration of the cost efficiency ofsubstrates or reactants, the reactivity or separability from products.By way of illustration, the amount of the phosphine chalcogenide is lessthan 1 mole (e.g., about 0.01 to 0.5 mole), and preferably about 0.05 to0.3 mole per mole of the material olefin. The amount of the noble metalcompound is less than 1 mole (e.g., about 0.01 to 0.5 mole), andpreferably about 0.05 to 0.2 mole per mole of the olefin. Theco-catalyst may be used in an amount of, for example, about 0.05 to 3.0moles, and preferably about 0.5 to 2.0 moles per mole of the olefin.

The amount of the alcohol used in the reaction is, per mole of theolefin, for example equal to or more than 2 moles, and preferably equalto or more than 2.5 moles. The alcohol can also serve as a reactionsolvent as well as a reactant.

In addition to the above mentioned alcohols, the reaction solventincludes, but not limited to, acetone and other ketones; tetrahydrofuranand other ethers; benzene, toluene and other aromatic hydrocarbons;hexane, octane and other aliphatic hydrocarbons; acetonitrile,propiononitrile and other nitrites; pyridine, triethylamine and otherbasic solvents; 1,2-dichloroethane and other halogenated hydrocarbons;amides; and esters. The reaction can be carried out either in thepresence of or in the absence of any solvent.

The amount of oxygen is usually equal to or more than 0.5 mole, and thatof carbon monoxide is usually equal to or more than 2 moles bothper moleof the olefin. Both oxygen and carbon monoxide are generally used inexcess with respect to the olefin. The ratio of carbon monoxide tooxygen is for instance such that the former : the latter ranges fromabout 5:95 to about 95:5, (by mole) and preferably from about 10:90 toabout 90:10 (by mole).

The reaction temperature and reaction pressure can suitably be selectedin consideration of the reactivity, operativity and cost efficiency. Thereaction temperature should fall, for example, in the range from about0° C. to about 200° C. and preferably from about 20° C. to about 150° C.The reaction is preferably carried out under ambient pressure, but canbe conducted under a pressurized condition. The reaction may be carriedout in a conventional manner such as in a batch system, semi-batchsystem or continuous system. After the completion of reaction, reactionproducts can readily be isolated and purified by a conventionalisolation and purification means including filtration, condensation,distillation, extraction, recrystallization or combinations of theseisolation means.

According to the above process (method), olefins can bebisalkoxycarbonylated with efficiency. In particular, aromatic olefinsand vinylsilanes can give bisalkoxycarbonyl derivatives in high yields.Even from aliphatic terminal olefins, corresponding bisalkoxycarbonylderivatives can be obtained in high yield. In addition, on reactingcyclic olefins conjugated with an aromatic ring, correspondingcis-diesters (cis-bisalkoxycarbonyl compounds) can selectively obtained.

A reaction according to the process (method) of the invention gives acorresponding succinate derivative (succinic acid ester derivative) froma material olefin in satisfactory yield. By way of example, the reactionof an olefin of the formula (2) with an alcohol of the formula (3),oxygen and carbon monoxide gives a succinate derivative of the formula(4).

Upon the use of a catalyst with the optically active phosphinechalcogenide as a ligand and an olefin, as a material, capable offorming a chiral compound by reaction, a corresponding optically activesuccinate derivative can be obtained.

The use of a 2-substituted propene derivative (e.g., a 2-silylpropenederivative) or the like as the olefin may result in the formation of1,3-bisalkoxycarbonyl compound (a glutarate derivative). This isprobably because of the elimination and re-insertion of β-hydrido in thereaction process. When an olefin having a hydroxyl group inthe molecule(e.g., an olefin having a hydroxyl group at the β- or γ-position carbonatom) is used as a material, an transesterification between onealkoxycarbonyl group of a succinate derivative once formed and thehydroxyl group proceeds to cyclization and hence a correspondingα-alkoxycarbonylmethyllactone is formed. By way of illustration, anolefin having a hydroxyl group at the β-position carbon atom gives acorresponding (α-alkoxycarbonylmethyl-γ-butyrolactone derivative. Inthis case, the use of a catalyst containing an optically active ligandcan provide an optically active lactone.

According to the catalyst of the invention, where a noble metal compoundis used in combination with a specific ligand, olefins can bebisalkoxycarbonylated with efficiency. The use of the novel phosphinechalcogenide of the invention as a ligand of a catalyst can attain theasymmetric bisalkoxycarbonylation of olefins.

According to the process and method of the invention, correspondingsuccinate derivatives from individual olefins can be obtained in highyield.

The present invention will be further illustrated in detail withreference to several examples below which are not directed to limitingthe scope of the invention. The yields of products in Examples 6 through8 were determined by gas chromatography. The optical purity of producedoptically active substances was determined by high performance liquidchromatography [Daicel Chemical Industries, Ltd., Chiralcel OD,hexane/2-propanol (15:1)].

EXAMPLE 1

Preparation of (2R,3R)-2,3-bis(diphenylthiophosphoryl)butane[(2R,3R)-ChiraphosS₂]

Under argon atmosphere, a mixture of(2R,3R)-(+)-2,3-bis(diphenylphosphino)butane [(2R,3R)-Chiraphos] (250mg, 0.59 mmol), elementary sulfur (121.6 mg, 3.79 mmol), and ether (20ml) was stirred at room temperature overnight. After removing excesssulfur by chromatography on a silica gel (eluent: hexane), fractionscontaining the titled compound were collected and condensed. Thecondensate was then subjected to the purification with a silica gel thinlayer chromatography for preparation to give a white crystal of thetitled compound (275.5 mg, 0.562 mmol).

¹H-NMR (CDCl₃) δ: 1.28 (6H, m), 3.47 (2H, m), 7.37-7.88 (20H, m);¹³C-NMR (CDCl₃) 5: 9.89, 31.52, 128.46, 128.74, 131.63, 131.97; ³¹p-NMR(CDCl₃) δ: 53.49; IR (KBr) (cm⁻¹): 1440, 1100, 760, 715, 700, 610 mp:213-214° C.

EXAMPLE 2

Preparation of(2R,3R)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylthiophosphoryl)butane[(2R,3R)-DIOPS₂]

The procedure of Example 1 was repeated to give the titled compound,except that(2R,3R)-(−)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane[(2R,3R)-DIOP] was used instead of(2R,3R)-(+)-2,3-bis(diphenylphosphino)butane.

¹H-NMR (CDCl₃) δ: 1.11 (6H, s), 2.56 (2H, ddd, J=2.0, 16.8, 13.8 Hz),2.89 (2H, ddd, J=7.6, 9.2, 16.8 Hz), 4.37-4.44 (2H, m), 7.37-7.49 (12H,m), 7.73-7.89 (8H, m); ³¹P-NMR (CDCl₃) δ: 40.27; IR (KBr) (cm⁻¹): 1440,1100.

EXAMPLE 3

Preparation of (R)-2,2′-bis(diphenylthiophosphoryl)-1,1′-binaphthyl[(R)-BINAPS₂]

The titled compound was prepared in a similar manner as in Example 1,except that (R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl[(R)-BINAP] was used instead of(2R,3R)-(+)-2,3-bis(diphenylphosphino)butane.

¹H-NMR (CDCl₃) δ: 6.60-6.72 (4H, m), 7.22-7.49 (14H, m), 7.60-7.80 (14H,m); ³¹P-NMR (CDCl₃) δ: 44.91; IR (KBr) (cm⁻¹): 1435, 1095.

EXAMPLE 4

Preparation of(2R,3R)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylselenophosphoryl)butane

Under argon atmosphere, a mixture of(2R,3R)-(−)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane[(2R,3R)-DIOP] (995.7 mg, 1.99 mmol), elementary selenium (2.5 g, 31.6mmol) and benzene (30 ml) was stirred at room temperature for 3 hours.The solid matters were filtered off, and the filtrate was then condensedto give a residue, which was purified by chromatography on a silica gel(eluent: hexane-ethyl acetate=8.2) and subsequent recrystallization fromethanol to yield a white needle crystal of the titled compound (625.9mg, 0.95 mmol).

¹H-NMR (CDCl₃) δ: 1.16 (6H, s), 2.58-2.69 (2H, m), 3.04 (2H, ddd, J=7.6,10.2, 14.9 Hz), 4.44-4.50 (2H, m), 7.37-7.44 (12H, m), 7.73-7.90 (8H,m); ³¹P-NMR (CDCl₃) δ: 31.96; IR (KBr) (cm⁻¹) 1435, 1380, 1235, 1100.

EXAMPLE 5

Preparation of m2R,t3R)-2, 3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphoryl) butane

A mixture of (2R,3R)-(−)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane[(2R,3R)-DIOP] (957.1 mg, 1.92immol), acetone (20 ml) and 35% by weighthydrogen peroxide aqueous solution (1 ml) was stirred at roomtemperature under argon atmosphere for 14 hours. The reaction mixturewas condensed to give a solid matter, which after recrystallization fromethanol-water mixture solvent (1 ml 1.40 ml) afforded the titledcompound (933.5 mg, 1.76 mmol).

¹H-NMR (CDCl₃) δ: 1.11 (6H, s), 2.61 (2H, ddd, J=6.6, 9.2, 15.8 Hz),2.87 (2H, ddd, J=5.0, 15.8, 15.8 Hz), 4.10-4.22 (2H, m), 7.41-7.53 (12H,m), 7.73-7.82 (8H, m); ³¹P-NMR (CDCl₃) δ: 30.30; IR (KBr) (cm⁻¹): 1435.

EXAMPLE 6

Into a 30-ml two neck eggplant type flask were charged, under argonatmosphere, palladium(II) chloride (17.7 mg, 0.1 mmol),triphenylphosphine sulfide (29.6 mg, 0.1 mmol) and methanol (5 ml), andthe mixture was stirred at room temperature forihour. Subsequently,copper(I) chloride (99.0mg, immol), styrene (155 μl, 1 mmol) andmethanol (5 ml) were added to the mixture. The atmosphere was replacedwith carbon monoxide-oxygen mixture gas (approximately 1:1 by volume,total pressure: 1 atm) and the mixture was then stirred at roomtemperature for 3 days. After the completion of reaction, a metalresidue was removed by a silica gel short column, and the product waspurified through PTLC (hexane:ethyl acetate=4:1) to give dimethyl2-phenylsuccinate (184.3 mg, 0.83 mmol, yield 83%).

¹H-NMR (CDCl₃) δ: 2.66 (1H, dd, J=5.28, 16.98), 3.21 (1H, dd, J=9.90,16.98), 3.64 (3H, s), 4.09 (1H, dd, J=5.28, 9.90), 7.24-7.35 (5H, m);³C-NMR (CDCl₃) δ: 37.47, 46.93, 51.70, 52.19, 127.53, 127.57, 128.74,137.52, 171.80, 173.25; IR (cm⁻¹): 1740, 1440, 1310, 1160, 1000; mp:54-56° C.

Colorless crystal.

EXAMPLE 7

The procedure of Example 6 was repeated, except that 0.1 mmol oftriphenylphosphine oxide was used instead of triphenylphosphine sulfide,to yield dimethyl 2-phenylsuccinate in a yield of 60%.

EXAMPLE 8

The procedure of Example 6 was repeated, except that 0.1 mmol oftriphenylphosphine selenide was used instead of triphenylphosphinesulfide, to give dimethyl 2-phenylsuccinate in a yield of 16%.

EXAMPLE 9

In a similar manner as in Example 6 except that 1 mmol of4-vinylbiphenyl was used instead of styrene and triphenylphosphinesulfide was employed in an amount of 0.2 mmol, dimethyl 2-(4-biphenyl)succinate was obtained in a yield of 51%.

¹H-NMR (CDCl₃) δ: 2.71 (1H, dd, J=5.49, 17.03), 3.24 (1H, dd, J=10.16,17.03), 3.68 (3H, s), 3.70 (3H, s), 4.14 (1H, dd, J=5.49, 10.16),7.25-7.58 (9H, m); ¹³C-NMR (CDCl₃) δ: 37.56, 46.72, 51.90, 52.42,127.01, 127.37, 127.57, 128.11, 128.75, 136.58, 140.46, 140.60, 171.93,173.36; IR (cm⁻¹) : 1740, 1490, 1330, 1240, 1160 mp: 103-104° C.

Colorless crystal.

EXAMPLE 10

Dimethyl 2-(p-methoxyphenyl)succinate was obtained in a yield of 82% ina similar manner as in Example 6, except that 1 mmol of p-methoxystyrenewas used instead of styrene, and triphenylphosphine sulfide was employedin an amount of 0.2 mmol.

¹H-NMR (CDCl₃) δ: 2.65 (1H, dd, J=5.49, 16.76), 3.17 (1H, dd, J=9.89,16.76), 3.66 (6H, s), 3.78 (3H, s), 4.04 (1H, dd, J=5.49, 9.89),6.83-6.88 (2H, m), 7.17-7.22 (2H, m); ¹³C-NMR (CDCl₃) δ: 37.65, 46.18,51.78, 52.25, 55.18, 114.18, 128.70, 129.61, 158.97, 171.96, 173.61; IR(cm⁻¹): 2960, 1740, 1515, 1380-1140.

Colorless oil.

EXAMPLE 11

Dimethyl 2-(p-chlorophenyl)succinate was afforded in a yield of 59% in asimilar manner as in Example 6, except that 1 mmol of p-chlorostyrenewas used instead of styrene, and triphenylphosphine sulfide was employedin an amount of 0.2 mmol.

¹H-NMR (CDCl₃) δ: 2.66 (1H, dd, J=5.77, 16.76), 3.18 (1H, dd, J=9.62,16.76), 3.17 (3H, s), 3.68 (3H, s), 4.07 (1H, dd, J=5.77, 9.62),7.20-7.32 (4H, m); ¹³C-NMR (CDCl₃) δ: 37.38, 46.40, 51.89, 52.43,128.98, 129.08, 133.57, 136.03, 171.61, 172.95; IR (cm⁻¹): 1740, 1490,1440, 1160, 1100.

Colorless oil.

EXAMPLE 12

Using 0.99 mmol of allylbenzene instead of styrene and employingtriphenylphosphine sulfide in an amount of 0. 2 mmol, dimethyl2-benzylsuccinate was obtained in a yield of 48% in a similar manner asin Example 6.

¹H-NMR (CDCl₃) δ: 2.40 (1H, dd, J=4.67, 17.03), 2.68 (1H, dd, J=8.79,17.03), 2.75 (1H, dd, J=7.97, 13.46), 3.05 (1H, dd, J=6.32, 13.46), 3.13(1H, m), 3.63 (3H, s), 3.66 (3H, s), 7.12-7.32 (5H, m); ¹³C-NMR (CDCl₃)δ: 34.59, 37.44, 42.73, 51.47, 51.63, 126.43, 128.26, 128.70, 137.82,171.97, 174.37; IR (cm⁻¹): 3100-2850, 1740, 1440, 1300-1140.

Colorless oil.

EXAMPLE 13

The procedure of Example 6 was repeated to give dimethyl2-(o-hydroxybenzyl)succinate in a yield of 70%, except that 1.09 mmol ofo-allylphenol was used instead of styrene.

¹H-NMR (CDCl₃) δ: 2.52 (1H, dd, J=5.77, 16.75), 2.75 (1H, dd, J=7.97,16.75), 2.82 (1H, dd, J=7.14, 13.73), 3.05 (1H, dd, J=7.14, 13.73), 3.23(1H, m), 3.65 (3H, s), 3.66 (3H, s), 6.79 (1H, s), 6.78-7.18 (4H, m);¹³C-NMR (CDCl₃) δ: 31.89, 35.27, 41.77, 51.99, 52.18, 116.08, 120.31,124.44, 128.18, 131.04, 154.40, 173.20, 175.61 IR (cm⁻¹): 3450, 1740,1460-1440.

Colorless oil.

EXAMPLE 14

Dimethyl cis-1,2-indanedicarboxylate was obtained in a yield of 29% in asimilar manner as in Example 6, except that 0.99 mmol of indene was usedinstead of styrene, triphenylphosphine was employed in an amount of 0.2mmol and the reaction time after replacement with carbon monoxide-oxygenwas changed to 14 days. ¹H-NMR (CDCl₃) δ: 3.15-3.21 (1H, m), 3.50-3.60(2H, m), 3.64 (3H, s), 3.73 (3H, s), 4.31-4.33 (1H, m), 7.17-7.37 (4H,m); ¹³C-NMR (CDCl₃) δ: 34.11, 47.28, 51.94, 52.04, 52.21, 124.82,124.92, 126.89, 128.19, 139.08, 142.44, 172.39, 172.94 IR (cm⁻¹):3100-2900, 1760-1720, 1590-1420, 1350-1020.

Colorless oil.

EXAMPLE 15

Dimethyl cis-1,2-tetralindicarboxylate was obtained in a yield of 35% ina similar manner as in Example 6, except that 1 mmol of1,2-dihydronaphthalene was used instead of styrene andtriphenylphosphine sulfide was employed in an amount of 0.2 mmol.

¹H-NMR (CDCl₃) δ: 2.08-2.32 (2H, m), 2.58-2.84 (3H, m), 3.48 (3H, s),3.56 (3H, s), 4.05 (1H, d, J=5.22); ¹³C-NMR (CDCl₃) δ: 20.98, 28.63,42.16, 45.24, 51.96, 52.07, 125.84, 127.34, 129.23, 129.94, 131.81,136.35, 172.85, 173.81; IR (cm⁻¹): 1740, 1440, 1260-1150.

Colorless oil.

EXAMPLE 16

Dimethyl 2-(dimethylphenylsilyl)succinate was obtained in a yield of 91%in a similar manner as in Example 6, except that 1 mmol ofdimethylphenylvinylsilane was used instead of styrene andtriphenylphosphine sulfide was employed in an amount of 0.2 inmol.

¹H-NMR (CDCl₃) δ: 0.39 (3H, s), 0.40 (3H, s), 2.25 (1H, dd, J=2.20,16.21), 2.71 (1H, dd, J=2.20, 11.81), 2.80 (1H, dd, J=11.81, 16.21),3.60 (6H, s), 7.30-7.60 (5H, m); ¹³C-NMR (CDCl₃) δ: −5.10, −3.90, 31.22,32.50, 51.22, 51.67, 127.88, 129.68, 133.66, 135.02, 173.13, 174.59; IR(cm⁻¹): 3100-2900, 1730, 1440, 840.

Colorless oil

EXAMPLE 17

The procedure of Example 6 was repeated, except that 1 mmol ofdimethylphenyl(1-propenyl)silane (E/Z =63/37) was used instead ofstyrene and triphenylphosphine sulfide was employed in an amount of 0.2mmol, to give dimethyl 2-(dimethylphenylsilyl)-3-methylsuccinate in ayield of 66% (syn/anti=77/23).

¹H-NMR (CDCl₃) δ: 0.40 (6H, s), 1.05 (major 3H, d, J=7.14), 1.05 (minor3H, d, J=6.87), 2.60 (major 1H, d, J=10.16), 2.60 (minor 1H, d,J=10.46), 2.80-3.00 (1H, m), 3.54 (3H, s), 3.63 (3H, s), 7.32-7.48 (5H,m); ¹³C-NMR (CDCl₃) δ: −3.55, −2.51, 17.44, 38.84, 40.71, 51.13, 51.85,127.76, 127.90, 129.55, 133.82, 134.06, 174.87, 174.50; IR (cm⁻¹): 2950,1740, 1720, 1430, 1160.

Colorless oil.

EXAMPLE 18

Using 1 mmol of isopropenyldimethylphenylsilane instead of styrene, andtriphenylphosphine sulfide in an amount of 0.2 mmol, dimethyl3-(dimethylphenylsilyl)glutarate was obtained in a yield of 61% in asimilar manner as in Example 6.

¹H-NMR (CDCl₃) δ: 0.32 (6H, s), 1.91 (1H, m), 2.29 (2H, dd, J=8.79,15.66), 2.43 (2H, dd, J=5.49, 15.93), 3.58 (6H, s), 7.34-7.56 (5H, m);¹³C-NMR (CDCl₃) δ: −4.68, 18.70, 34.43, 51.50, 127.84, 129.82, 133.92,136.46, 173.62; IR (cm⁻¹): 2960, 1740, 1440.

Colorless oil.

EXAMPLE 19

Except using 1 mmol of o-chlorostyrene instead of styrene, andtriphenylphosphine sulfide in an amount of 0.2 mmol, dimethyl2-(o-chlorophenyl)succinate was obtained in a yield of 26% in a similarmanner as in Example 6.

¹H-NMR (CDCl₃) δ: 2.68 (1H, dd, J=5.22, 17.03), 3.15 (1H, dd, J=9.89,17.03), 3.69 (3H, s), 3.71 (3H, s), 4.61 (1H, dd, J=5.22, 9.89),7.18-7.45 (4H, m); ¹³C-NMR (CDCl₃) δ: 36.43, 43.98, 51.89, 52.45,127.24, 128.81, 128.90, 129.97, 133.64, 135.63, 171.71, 172.83 (cm¹7):1740, 1440, 1170.

Colorless oil.

EXAMPLE 20

The procedure of Example 6 was repeated to give methyl1-(3-isochromanonyl) acetate in a yield of 25%, except that 1.01 mmol ofo-vinylbenzyl alcohol was used instead of styrene and triphenylphosphinesulfide was employed in an amount of 0.2 mmol.

¹H-NMR (CDCl₃) δ: 3.15 (2H, ddd, J=6.59, 16.75, 32.41), 3.76 (3H, s),3.76-3.80 (1H, m), 4.09-4.14 (1H, m), 5.35 (2H, dd, J=13.74, 37.09),7.17-7.69 (4H, m); ¹³C-NMR (CDCl₃) δ: 32.00, 41.07, 52.15, 69.36,123.94, 124.93, 127.35, 128.90, 171.82, 171.89; IR (cm⁻¹): 1760-1720,1440, 1150.

Colorless oil.

EXAMPLE 21

Except that 1.01 mmol of 5-phenyl-1-pentene was used instead of styrene,methyl 3-methoxycarbonyl-6-phenylhexanoate was obtained in a yield of28% in a similar manner as in Example 6.

¹H-NMR (CDCl₃) δ: 1.52-2.00 (4H, m), 2.20-2.95 (5H, m), 3.66 (3H, s),3.69 (3H, s), 7.12-7.32 (5H, m); ¹³C-NMR (CDCl₃) δ: 28.65, 31.41, 35.47,35.76, 40.93, 51.71, 51.78, 125.78, 128.26, 128.30, 128.34, 172.29,175.24; IR (cm⁻¹): 1740, 910, 740.

Colorless oil.

EXAMPLE 22

Except using 1 mmol of t-butyl acrylate instead of styrene, andtriphenylphosphine sulfide in an amount of 0.2 mmol, the procedure ofExample 6 was repeated to give dimethyl 2-(t-butoxycarbonyl)succinate ina yield of 34%.

EXAMPLE 23

Into a 30-ml two necked eggplant type flask were charged, under argonatmosphere, palladium(II) chloride (8.9 mg, 0.05 mmol),(2R,3R)-2,3-bis(diphenylthiophosphoryl)butane [(2R,3R)-ChiraphosS₂](27.0 mg, 0.06mmol), copper(II) acetate (142.0 mg, 0.78 mmol),1,1-diphenyl-3-buten-1-ol (111.6 mg, 0.5 mmol) and methanol (4 ml).After replacing the inside atmosphere with a gaseous mixture of carbonmonoxide-oxygen (approximately 1:1 by volume, total pressure: 1 atm),the charged was stirred at room temperature for 3 days. After thecompletion of reaction, a metal residue was removed by a silica gelshort column, and the product was purified through PTLC (hexane:ethylacetate=4:1) to give2-(methoxycarbonylmethyl)-4,4-diphenyl-y-butyrolactone (100.7 mg, 0.32mmol, yield 65%, optical purity 14% ee).

EXAMPLE 24

Into a 30-ml two necked eggplant type flask were placed, under argonatmosphere, palladium(II) trifluoroacetate (16.2 mg, 0.05 mmol),(lS,2S,3S,4S)-1,2-bis(diphenylthiophosphorylmethyl)-3,4-bis(2-methoxyphenyl)cyclobutane[(1S,2S,3S,4S)-CDPS₂)] (40.5 mg, 0.06 mmol) and methanol (2 ml), and themixture was stirred at room temperature for 1 hour. To the mixture werethen added copper(II) acetate (138.6 mg, 0.76 mmol),1,1-diphenyl-3-buten-1-ol (112.0 mg, 0.5 mmol) and methanol (2 ml), theinner atmosphere was replaced with a gaseous mixture of carbonmonoxide-oxygen (about 1:1 by volume, total pressure: 1 atm), and thecharged was stirred at room temperature for 3 days. After the completionof reaction, a metal residue was removed by a silica gel short column,and the product was purified through PTLC (hexane:ethyl acetate=4:1) toafford 2-(methoxycarbonylmethyl)-4,4-diphenyl-γ-butyrolactone (123.9 mg,0.40 mmol, yield 80%, optical purity 36% ee).

EXAMPLE 25

Into a 30-ml two necked eggplant type flask were placed, under argonatmosphere, palladium(II) chloride (8.1 mg, 0.05 mmol),(1S,2S,3S,4S)-1,2-bis(diphenylthiophosphorylmethyl)-3,4-bis(2-methoxyphenyl)cyclobutane[(1S,2S,3S,4S)-CDPS₂] (35.8 mg, 0.05 mmol) and methanol (2 ml), and themixture was stirred at room temperature for 1 hour. To the mixture werethen added copper(I) chloride (75.8 mg, 0.77 mmol),1,1-diphenyl-3-buten-1-ol (112.0 mg, 0.5 mmol) and methanol (2 ml), theinner atmosphere was replaced with a gaseous mixture of carbonmonoxide-oxygen (about 1:1 by volume, total pressure: 1 atm), and thecharged was stirred at room temperature for 3 days. After the completionof reaction, a metal residue was removed by a silica gel short column,and the product was purified through PTLC (hexane:ethyl acetate 4:1) togive 2-(methoxycarbonylmethyl)-4,4-diphenyl-y-butyrolactone (143.7 mg,0.46 mmol, yield 86%, optical purity 35% ee).

EXAMPLE 26

Into a 30-ml two necked eggplant type flask were placed, under argonatmosphere, palladium(II) chloride (17.7 mg, 0.10 mmol),(1S,2S,3S,4S)-1,2-bis(diphenylthiophosphorylmethyl)-3,4-bis(2-methoxyphenyl)cyclobutane[(1S,2S,3S,4S)-CDPS₂] (72.9 mg, 0.10 mmol) and methanol (5 ml), and themixture was stirred at room temperature for 1 hour. To the mixture werethen added copper(I) chloride (99.3 mg, 1.00 mmol),dimethylphenylvinylsilane (163.5 mg, 1.01 mmol) and methanol (5 ml), theinner atmosphere was replaced with a gaseous mixture of carbonmonoxide-oxygen (about 1:1 by volume, total pressure: 1 atm), and thecharged was stirred at room temperature for 3 days. After the completionof reaction, a metal residue was removed by a silica gel short column,and the product was purified through PTLC (hexane:ethyl acetate=4:1) toafford dimethyl 2-(dimethylphenylsilyl)succinate (193.8 mg, 0.69 mmol,yield 69%, optical purity 18% ee).

EXAMPLE 27

Into a 30-ml two necked eggplant type flask were placed, under argonatmosphere, palladium(II) chloride (17.7 mg, 0.10 mmol),(R)-2,2′-bis(diphenylthiophosphoryl)-1,1′-binaphthyl [(R)-BINAPS₂] (68.7mg, 0.10 mmol) and methanol (5 ml), and the mixture was stirred at roomtemperature for 1 hour. To the mixture were then added copper(I)chloride (99.0mg, 1.00 mmol), dimethylphenylvinylsilane (166.8 mg, 1.03mmol) and methanol (5 ml), the inner atmosphere was replaced with agaseous mixture of carbon monoxide-oxygen (about 1:1 by volume, totalpressure: 1 atm), and subsequently the charged was stirred at roomtemperature for 3 days. After the completion of reaction, a metalresidue was removed by a silica gel short column, and the product waspurified through PTLC (hexane:ethyl acetate=4:1) to afford dimethyl2-(dimethylphenylsilyl)succinate (195.2 mg, 0.70 mmol, yield 70%,optical purity 24% ee).

EXAMPLE 28

Into a 30-ml two necked eggplant type flask were placed, under argonatmosphere, palladium(II) chloride (17.8 mg, 0.10 mmol),methyldiphenylphosphine sulfide (46.5 mg, 0.20 mmol) and methanol (5ml), and the mixture was stirred at room temperature for 1 hour. To themixture were then added copper(I) chloride (99.8 mg, 1.00 mmol), styrene(104.0 mg, 1.00 mmol) and methanol (5 ml), the inner atmosphere wasreplaced with a gaseous mixture of carbon monoxide-oxygen (about 1:1 byvolume, total pressure: 1 atm), and subsequently the charged was stirredat room temperature for 3 days. After the completion of reaction, ametal residue was removed by a silica gel short column, and the productwas purified through PTLC (hexane:ethyl acetate 4:1) to give dimethyl2-phenylsuccinate in a yield of 17%.

EXAMPLE 29

Into a 30-ml two necked eggplant type flask were placed, under argonatmosphere, palladium(II) chloride (26.4 mg, 0.15 mmol),methyl(l-naphthyl)phenylphosphine sulfide (85.6 mg, 0.30 mmol) andmethanol (5 ml), and the mixture was stirred at room temperature for 1hour. To the mixture were then added copper(I) chloride (148.0 mg, 1.50mmol), styrene (156.0 mg, 1.50 mmol) and methanol (5 ml), the inneratmosphere was replaced with a gaseous mixture of carbon monoxide-oxygen(about 1:1 by volume, total pressure: 1 atm), and subsequently thecharged was stirred at room temperature for 3 days. After the completionof reaction, a metal residue was removed by a silica gel short column,and the product was purified through PTLC (hexane:ethyl acetate=4:1) togive dimethyl 2-phenylsuccinate in a yield of 36%.

EXAMPLE 30

Into a 30-ml two necked eggplant type flask were placed, under argonatmosphere, palladium(II) chloride (0.1 mmol), (R)-2,2′-bis(diphenylthiophosphoryl)-1,1′-binaphthyl [(R)-BINAPS₂] (0.1 mmol) andmethanol (5 ml), and the mixture was stirred at room temperature for 1hour. To the mixture were then added copper(I) chloride (1 mmol),styrene (1 mmol) and methanol (5 ml), the inner atmosphere was replacedwith a gaseous mixture of carbon monoxide-oxygen (about 1:1 by volume,total pressure: 1 atm), and subsequently the charged was stirred at roomtemperature for 3 days. After the completion of reaction, a metalresidue was removed by a silica gel short column, and the product waspurified through PTLC (hexane: ethyl acetate=4:1) to afford dimethyl2-phenylsuccinate (yield 48%, optical purity 8% ee).

EXAMPLE 31

Dimethyl 2-phenylsuccinate (yield 41%, optical purity 24% ee) wasobtained in a similar manner as in Example 30, except that 0.1 mmol of(2R,3R)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylthiophosphoryl)butane[(2R,3R)-DIOPS₂] was used instead of(R)-2,2′-bis(diphenylthiophosphoryl)-1,1′-binaphthyl.

EXAMPLE 32

Dimethyl 2-phenylsuccinate (yield 68%, optical purity 30% ee) wasobtained in a similar manner as in Example 30, except that 0.1 mmol of(2R,3R)-2,3-bis (diphenylthiophosphoryl)butane [(2R, 3R)-ChiraphosS₂]was used instead of(R)-2,21-bis(diphenylthiophosphoryl)-1,1′-binaphthyl.

As many apparently widely different embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that the invention is not limited to the specific embodimentsthereof except as defined in the appended claims.

What is claimed is:
 1. A process for the bisalkoxycarbonylation ofolefins comprising the step of reacting an olefin with an alcohol,oxygen and carbon monoxide in the presence of a catalyst for thebisalkoxycarbonylation of olefins comprising a noble metal compound anda phosphine chalcogenide of the following formula (1):

wherein each of R¹, R² and R³ is, independently, an alkyl group or anaryl group each of which optionally has a substituent, and A is a Group16 element of the Periodic Table; and R¹, R² or R³ are optionallycombined, directly or through a bridging group, with one another wherethe groups to be combined are optionally attached either to the samephosphorus atom or to a different phosphorus atom.
 2. A method ofproducing a succinate derivative comprising the step of reacting anolefin with an alcohol, oxygen and carbon monoxide in the presence of acatalyst for the bisalkoxycarbonylation of olefins to form acorresponding succinate derivative, said catalyst comprising a noblemetal compound and a phosphine chalcogenide of the following formula(1):

wherein each of R¹, R² and R³ is, independently, an alkyl group or anaryl group each of which optionally has a substituent, and A is a Group16 element of the Periodic Table; and R¹, R² or R³ are optionallycombined, directly or through a bridging group, with one another wherethe groups to be combined are optionally attached either to the samephosphorus atom or to a different phosphorus atom.
 3. The methodaccording to claim 2, wherein an olefin of the following formula (2):

wherein each of R⁴, R⁵ and R⁶ is, independently, a hydrogen atom, analkyl group which optionally has a substituent, an aryl group whichoptionally has a substituent, or a substituted silyl group, and at leasttwo of R⁴, R⁵ or R⁶ optionally together form a ring with an adjacentcarbon atom or carbon-carbon double bond, with an alcohol of thefollowing formula (3): R⁷—OH  (3) wherein R⁷ is an alkyl group, acycloalkyl group or an aryl group each of which optionally has asubstituent, oxygen and carbon monoxide to form a succinate derivativeof the following formula (4):

wherein R⁴, R⁵, R⁶ and R⁷ have the same meaning as defined above.
 4. Themethod according to claim 3, wherein an olefin is subjected to thereaction in which R⁴ is a hydrogen atom or an alkyl group whichoptionally has a substituent, either one of R⁵ and R⁶ is a hydrogen atomor an alkyl group which optionally has a substitutent, and the other isan aryl group which optionally has a substituent, or a substituted silylgroup, and R⁴ and R⁶ optionally together form a ring with the adjacentcarbon-carbon double bond.
 5. The method according to claim 2, whereinan olefin is reacted with an alcohol, oxygen and carbon monoxide in thepresence of a catalyst containing an optically active phosphinechalcogenide to form a corresponding optically active succinatederivative.